Process and composition for treating keratinous material



Patented Feb. 6, 1951 PROOESS AND COMPOSITION FOR TREAT- ING KERATINOUSMATERIAL Marion Den Beste and Raymond E. Reed, St. Paul, Minn.,assignors to Raymond Laboratories, Inc., F St. Paul, Minn., acorporation of Minnesota No Drawing. Application October 16, 1946,Serial No. 703,476

23 Claims.

The present invention relates to compositions particularly useful fortreating keratin-containing materials, such as hair and wool, and toprocesses employing such compositions for treating keratin materials toalter their chemical and physical properties.

Wool, hair, fur and like epidermal materials are characterized by thepresence therein of the fibrous protein, keratin. Keratin is comprisedof polypeptide chains joined together by cystine linkages. In recentyears there have been proposed many processes for changing the chemicaland physical properties of naturally-occurring keratin-containingmaterials by chemical treatment involving splitting of the cystinelinkages of the keratin. Processes for the permanent waving of humanhair or for straightening human hair, for example, fall in thiscategory, and the invention will be described with particular referenceto hair waving, although it will be understood that it is applicablegenerally to the treatment of keratin-containing materials and toarticles fabricated therefrom.

In the permanent waving of human hair it is well recognized that some ofthe cystine linkages present in the keratin structure must be split inorder to permit the development of a wave undulation. To this end, thehair is usually treatedwith a suitable reducing agent while it is heldunder stress in a coiled or curled condition. The splitting of cystinelinkages permits a reorientation of the polypeptide chains to relievethe stress and this accounts for the development of the wave undulation.Thereafter it is essential that the action of the reducing agent bearrested and that linkages in the keratin structure be rebuilt,otherwise the wave undulation will not be permanent.

The preferred reagents for keratin cystine linkage attack have beencompounds in the mercaptan family or compounds having a sulflte radical.In the first classification, thioglycollates enjoy a wide application,and in the second classification, alkali metal sulfites and aminesulfites are extensively used. In the so-called cold permanent wavingprocess an aqueous solution of ammonium thioglycollate has been apreferred selection as the processing solution. After the usualshampooing operation, the hair is treated with this preparation and isthen wrapped around a rod of small diameter. After a suitable processingperiod, which varies with the condition and texture of the hair, a Waveundulation develops.

Despite the excellent acceptance of the cold permanent waving process,certain fundamental 2 defects in this treatment are well recognized. Onesuch defect is the large incidence of waving failures which are a resultof the difficulty associated with forcing an oxidizing agent uniformlythrough a wrapped tress which is already saturated with cold wavingsolution; Also, the action of the reducing solution is diflicult tocontrol and overprocessing of the hair is quite common. Further, thesedefects include the fear that sulfhydryl compounds might be absorbed.through the skin and induce systemic reactions in the human body.

An object of the present invention is to provide improved processes foraltering the chemical and physical properties of keratin materialsthrough rupture of cystine linkages therein. Another object of theinvention is to provide compositions, useful in treating keratinmaterials in processes of this character, which do not necessitatesubsequent application of a separate oxidizing solution to the keratinmaterial. Another object is to provide improved cold permanent wavingprocesses and hair treating lotions for use in such processes.

The compositions of the present invention have the desired reducingproperties when applied to keratin containing material but areinherently auto-oxidizing and self-limiting in their effect. Asreduction by these compositions pro ceeds, a second reaction whichdestroys the reducing power of the solution takes place. Thesecompositions permit the formation of hair waving lotions, for example,which will give an optimum reducing effect but which need not befollowed by the usual separate oxidizing treatment and which at the sametime minimize the incidence of waving failures, the hazards of skinirritation and toxic effects, and the hazard of overprocessing.

The invention involves treatment of the keratin material with a materialwhich functions as an oxidation catalyst in the environment provided bythe keratin and the reducing agent.

In accordance with one aspect of the invention, the substantiveproperties of keratin are made use of to permit pretreatment of hair,for example, with a suitable catalytic agent to form an association withthe hair which is sufficiently stable to resist normal rinsingoperations and to remain effective during subsequent steps of the wavingtreatment. For this purpose, we may use, for example, an aqueoussolution of magnanese chloride containing 200 parts per million ofmanganese. The treated hair can then be subjected to the action of asuitable reducing agent, or

may be dried before application of the reducin agent. Under theinfluence of the catalytic agent and atmospheric oxygen, the reducingcapacity of the reducing agent is gradually lessened and the liquid incontact with the hair is gradu-' ally converted to an oxidizing mediumwhich brings about rebuilding of cystine linkages.

In accordance with another aspect of the invention, the reagent forcontrolling the effect of the reducing agent may be combined with thereducing agent. When this combination is applied to the keratin, as inhair waving, the reduction proceeds to a desired extent before it isovercome by the'oxidation reaction characteristic of my novelcomposition. This oxidation destroys the reducing power of the solutionand promotes rebuilding of cystine linkages in the keratin structure.This linkage rebuilding renders the ph sical changes which have beeneffected in the keratin structure permanent for all practical purposes.

The following examples illustrate various applications of the inventionto the permanent waving of hair:

The hair is shampooed in the usual way and excess water squeezed out.Then from 4 to 32 ounces of a liquid solution of manganese chloride anda wetting agent is poured through the hair. 'The concentration of themanganese may be from 50 parts per million (0.005%) in 32 ounces to1,000 parts per million (0.1%) in 4 ounces. A

suitable wetting agent is aerosol AY which may tion may comprise:

Ammonium thioglycollate 0.7 normal Ammonium hydroxide 0.7 normal Thislotion has a pH of about 9.3.

The waving lotion is allowed to remain in the wrapped tresses until acurl pattern is developed. The skilled operator will readily determinethe length of this period in accordance with the "condition and type ofthe hair and the strength of the lotion. Two hours would be an adequateperiod of time for the 0.7 normal lotion described. Finally, the curlsare unwound and the hair is flufled, rinsed in tepid water and styled asdesired.

The action of the atmospheric oxygen on th hair and on the lotion can beaccelerated by removing excess lotion from the hair after the 10- tionhas been in contact with the hair long enough to cause a curl pattern tobe developed. Removal of excess lotion facilitates access of atmosphericair to the hair and increases the diffusion rate of oxygen into theliquid phase of the system, whereby conversion of the liquid to anoxidizing medium is promoted at a more rapid rate, thus shortening thetime required for the waving process. Any convenient means fordehydrating may be employed; for example, a towel may be used to removeexcess liquid from the hair. A more effective method of dehydrating thehair is through the application of absorbent pads to the individualtresses. Also, the usual hair drying devices commonly found in beautyshops may be employed for this purpose. It will be understood that thisstep of removing excess liquid may be employed, if desired, in theprocess of the foregoing example 4 and also may be employed in theprocesses described in the following examples.

The following example is given as illustrative of a hair waving processin which the manganese is incorporated in the shampoo and a dehydratingstep is employed.

Shampoo the hair, making three applications of fresh shampoo containingmanganous chloride in amount sufiicient to give a concentration ofmanganese between 500 and 2,000 mg. per liter (0.05-0.2%). Approximately4 ounces of shampoo should be used. During this operation manganese isdeposited on or in the hair due to the substantive properties of thekeratin. Thereafter the hair is rinsed and then is sectioned, blocked,wrapped, treated with waving lotion, dried, rinsed and styled asdescribed above.

The following example illustrates a hair waving process employing anovel composition of the present invention. The hair is shampooed withan ordinary shampoo material, rinsed thoroughly, and then sectioned,blocked and wrapped on cold waving rods. The wrapped tresses are thentreated with an aqueous waving lotion comprising the following:

Ammonium thioglycollate 0.7 normal Ammonium hydroxide 0.7 normalHydrated manganous chloride parts per million" 720 Aerosol AY (wettingagent) per cent 0.6

This lotion has a pH of about 9.3.

After the curl pattern has developed properly the tresses are pressedwith a dry towel to remove excess liquid. Thereafter absorbent pads areplaced over each curl to remove excess liquid and admit air to fix thewave. The absorbent pads may be of any suitable absorbent material,such, for example, as blotting paper, fabrics, or a material preparedfrom bleached cotton fibers which have been converted into unwovenfabric of the type and in the manner set forth in United 'States PatentNo. 2,277,049. As the liquid is removed from between the hair fibres,air gains entrance and serves, in the presence of the metal catalyst, tonullify the effect of the reducing solution. After about fifteenminutes, the absorbent pads are removed, the curls are unwound and thehair is fluffed and rinsed in tepid water and styled as desired.

In the processes of the foregoing examples a waving solution containingthioglycollate is employed. Instead of this solution, a solution inwhich the active reducing agent is a sulphite can be used. such asolution may contain Parts Sodium sulphite 11.34 Water 200 Ammoniumcarbonate 13 The ammonium carbonate acts as a buffer to maintain the pHat about 9. The solution may contain cobalt chloride in concentration ofabout parts per million.

-The preferred catalytic agent for the thioglycollate waving solution ismanganese, which may be present in the form of a solution of one of itswater soluble salts. For the sulphite waving solution, the preferredcatalytic agent is cobalt.

We have also found that copper, iron, and to a somewhat lesser extentnickel, are effective.

.These metals are employed in a form to make the metallic ionsavailable, for example in the form of water-soluble salts.

The period of time for which the lotion containing a catalytic agent ispermitted to remain in the wrapped curls may be varied and this periodwill depend to some extent upon the relative concentrations of thecatalytic agent and the reducing agent as well as upon the type ofreducing agent. For solutions to be used in the beauty parlor; thislotion may be formulated to remain in contact with the hair for a periodfrom a few minutes up to about half an hour. For home use this periodmay be increased.

The proportion of manganese or manganese compound in the waving lotionshould be such as to give a manganese concentration of from about 25parts per million (0.0025%) to 500 parts per million (0.05%) by weight.This range will vary somewhat depending upon the reducing agentincluded. With thioglycollates we prefe r to use proportions ofmanganese salts such as to give a concentration of manganese from 100parts per million to 300 parts per million.

In the system described, manganese appears to function as an oxidationcatalyst. In place of a normally slow oxidation of the reducing agent onexposure to air, a rapid oxidation takes place. From a chemicalstandpoint, the ammonium thioglycollate is converted to diammoniumdithioglycollate. As long as air is available this chemical change isstable and a hydrolytic reversion of the diammom'um dithioglycollate toammonium thioglycollate does not take place.

Although it is true that ammonium thioglycollate solutions oxidize uponexposure to air, the

rate of this reaction with reduced intact keratin fibres is such that itcannot be relied upon to destroy the reducing power of the solution. In

fact, event after prolonged exposure, the equilibrium obtained inaccordance with the law of mass action allows for the presence ofappreciable quantities of the sulfhydryl compound.

The present invention goes a long way toward solving the difl'icultiesassociated with the cold waving process. Any cold waving lotionaccidentall spilled on the scalp will be rapidly oxidized due to thecatalytic effect of the manganese, cobalt or other metal. On the otherhand, hair in the coiled state undergoing waving will process in thedesired manner because the difiusion rate of oxygen into the liquidphase of the system is limited by the surface of the curl exposed to theatmosphere. In other words, these conditions are desirably differentfrom those holding when the lotion is spilled and spreads into a thinfilm on the scalp.

Our invention is also applicable to keratolytic treatments such asdepilation of human hair and corn removal.

From the standpoint of overprocessing, the manganese-treated hairprevents the usual progressive reduction action, from continuing for toolong a period. The diffusion of oxygen into the coiled tress, althoughslow, is adequate to accomplish a desirable slowing up of the wavingaction as the desired curl strength is approached.

We claim:

1. A method of permanently changing the configuration of human hair uponthe head without appreciable damage to the hair structure, whichcomprises imparting the desired configuration to the hair, subjectingthe hair to treatment with a keratin reducing agent in the presence ofan oxidation catalyst, said oxidation catalyst being present in the hairat least from the commencement of said treatment, until the desiredconfiguration is obtained and then exposing the hair to atmosphericoxygen to oxidize the reducing agent by the action of the atmosphericoxygen in the presence of the oxidation catalyst and thereby fix thedesired configuration.

2. A method of permanently changing the configuration of human hair uponthe head without appreciable damage to the hair structure, whichcomprises imparting the desired configuration to the hair, subjectingthe hair to treatment with a keratin reducing agent in the presence of ametallic oxidation catalyst, said oxidation catalyst being present inthe hair at least from the commencement of said treatment, until thedesired configuration is obtained and then exposing the hair toatmospheric oxygen to oxidize the reducing agent by the action of theatmospheric oxygen in the presence of the oxidation catalyst and therebyfix the desired configuration.

3. A method of permanently changing the configuration of human hair uponthe head without appreciable damage to the hair structure, whichcomprises treating the hair with an aqueous solution containing not over0.2% of a metallic oxidation catalyst, expressed as free metal,imparting the desired configuration to the hair, then treating the hairwith a keratin reducing agent at a pH above about 9 until the desiredconfiguration is obtained. and then exposing the hair to atmosphericoxygen to oxidize the reducing agent by the action of the atmosphericoxygen in the presence of the oxidation cataly't and thereby fix theconfiguration.

4-. A method of permanently changing the configuration of human hairupon the head without appreciable damage to the hair structure, whichcomprises imparting the desired configuration to the hair, treating thehair with an aqueous solution containing a keratin reducing agent andnot more than 0.05% of a metallic oxidation catalyst, ex ressed as freemetal, at a pH value above about 9, until the desired configuration isobta ned. and then exposing the hair to atmospheric oxygen to oxidizethe reducing agent by the action of the atmospheric oxygen in thepresence of the oxidation catalyst and thereby fix the configuration.

5. The method of claim 1, in which the keratin reducing agent employedis an alkaline thioglycolate, at a pH value above about 9.

6. The method of claim 3 in which the metallic oxidation catalyst is awater soluble manganese salt and the keratin reducing agent employed isan aqueous solution containing ammonium thioglycolate.

7. The method of claim 3 in which the oxidation catalyst employed is awater soluble iron salt and the keratin reducing agent is an aqueoussolution containing ammonium thioglycolate.

8. The method of claim 3 in which the oxidation catalyst employed is awater soluble cobalt salt and the keratin reducing agent is an aqueoussolution containing ammonium thioglycolate.

9. The method of claim 4 in which the oxidation catalyst employed is awater soluble manganese salt and the keratin reducing agent an aqueoussolution containing ammonium thioglycolate.

10. The method of claim 4 in which the oxidation catalyst employed is awater soluble iron salt and the keratin reducing agent an aqueous;solution containing ammonium thioglycolate.

11. The method of claim 4 in which the oxidation catalyst employed is awater soluble cobalt salt and the keratin reducing agent an aqueoussolution containing ammonium thioglycolate.

12. A' permanent waving composition for changing the configuration ofhuman hair upon the head without appreciable damage to the hairstructure, comprising a keratin reducing agent in an efiective hairwaving concentration and not more than about 0.05% of a metallicoxidation catalyst, expressed as free metal, said composition having apH value above about 9, whereby oxidation of the keratin reducing agentmay be effected after the configuration of the hair has been permanentlychanged by treatment therewith, by exposure of the hair to atmosphericoxygen without use of additional oxidizing agents.

13. The product of claim 12 in which the oxidation catalyst is a watersoluble manganese salt.

14. The product of claim 12 in which the oxidation catalyst is a watersoluble iron salt.

15. The product of claim 12 in which the oxidation catalyst is a watersoluble cobalt salt.

16. The product of claim 12 in which the oxidation catalyst is a watersoluble manganese salt and the keratin reducing agent an aqueoussolution containing ammonium thioglycolate.

17. The product of claim 12 in which the oxidation catalyst is a watersoluble iron salt and the keratin reducing agent an aqueous solutioncontaining ammonium thioglycolate.

18. The product of claim 12 in which the oxidation catalyst is a Watersoluble cobalt salt and the keratin reducing agent an aqueous solutioncontaining ammonium thioglycolate.

19. The method of claim 1 in which the keratin reducing agent employedis a mercaptan.

20. The product of claim 12 in which the keratin reducing agent employedis a mercaptan.

21. The product of claim 12 in which the oxidation catalyst is a watersoluble manganese salt and the keratin reducing agent is an aqueoussolution containing ammonium thioglycolate in a concentration of about0.7 normal.

22. The product of claim 12 in which the oxidation catalyst is a watersoluble iron salt and the keratin reducing agent is an aqueous solutioncontaining ammonium thioglycolate in a concentration of about 0.7normal.

23. The product of claim 12 in which the oxidation catalyst is a watersoluble cobalt salt and the keratin reducing agent is an aqueoussolution containing ammonium thioglycolate in a concentration of about0.7 normal.

MARION DEN BESTE. RAYMOND E. REED.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 57,649 Du Motay Aug. 28, 18662,180,262 Sturm Nov. 14, 1939 2,181,121 Downing Nov. 28, 1939 2,193,173Jellinek Mar. 12, 1940 2,261,094 Speakman Oct. 28, 1941 2,376,186Rapkine May 15, 1945 FOREIGN PATENTS Number Country Date 692,981 FranceNov. 13, 1930 OTHER REFERENCES Whitmore, Organic Chemistry, D. VanNostrand, New York, 1937, pages 598, 599. (Book available in Pat. O11.Sci. Lib.)

Hall, Monthly Review, Textile Colorist, Aug. 1944, pages 318,319.

Hopkins, Glutathione," Biochemical J vol. 19 (1925), pages 787-819, page788 considered especially pertinent. (J. in Library of Congress.)

Goddard, Derivatives of Keratin, Journal of Biolog. Chem., vol. 112,Dec. 1935-Jan. 1936, pages 3611371; pages 362 and 367 considered esp.pertinen Swank, The Determination of Iron With Mercaptoacetic Acid, Ind.& Eng. Chem., Andl. ed., vol. 10, 1938, pages 7-9.

Snell, Colorimetric Methods of Analysis, second ed., vol. 1, 1936, pages298-300.

Tompsett, Thiolacetic Acid as a Reagent for the Determination of theInorganic Iron Content of Certain Biological Materials, BiochemicalJour., vol. 28, 1934, pages 1536-1549.

Lyons, Thioglycolic Acid as a Color Test for Iron, J. Am. Chem. Soc.,vol. 49, 1927, pages 1916-1920.

Cannan, The Thiol-Disulphide System, Biochemical, Jour., vol. 23, 1929,pages 1242-1262.

1. A METHOD OF PREMANENTLY CHANGING THE CONFIGURATION OF HUMAN HAIR UPONTHE HEAD WITHOUT APPRECIABLE DEMAGE TO THE HAIR STRUCTURE, WHICHCOMPRISES IMPARTING THE DESIRED CONFIGURATIN TO THE HAIR, SUBJECTING THEHAIR TO TREATMENT WITH A KERATIN REDUCING AGENT IN THE PRESENCE OF ANOXIDATION CATALYST, SAID OXIDATION CATALYST BEING PRESENT IN THE HAIR ATLEAST FROM THE COMMENCEMENT OF SAID TREATMENT, UNTIL THE DESIREDCONFIGURATION IS OBTAINED AND THEN EXPOSING THE HAIR TO ATMOSPHERICOXYGEN TO OXIDIZE THE REDUCING AGENT BY THE ACTION OF THE ATMOSPHERICOXYGEN IN THE PRESENCE OF THE OXIDATION CATALYST AND THEREBY FIX THEDESIRED CONFIGURATION.